Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand.
Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand.
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DOI：
10.1038/ncomms12181
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发表时间：
2016-07-20
影响因子：
16.6
通讯作者：
Nishibayashi Y
中科院分区：
文献类型：
--
作者：
Kuriyama S;Arashiba K;Nakajima K;Matsuo Y;Tanaka H;Ishii K;Yoshizawa K;Nishibayashi Y
铁原子在工业固氮和生物固氮中起着重要的作用，因此铁-氮络合物的合成及其反应活性得到了广泛的研究。因此，最近已经实现了铁催化将分子氮还原为氨。在这里，我们展示了一种含有阴离子PNP-钳形配体的铁-氮络合物作为催化固氮的有效催化剂，在那里产生了氨和联氨的混合物。在本反应体系中，以过渡金属氮络合物为催化剂，将分子氮直接催化转化为肼。由于肼被认为是固氮酶固氮的关键中间体，本文的研究结果为阐明固氮酶的反应机理提供了机会。将氮素转化为氨等其他氮化合物是一项艰巨的任务，尤其是在温和的条件下。在这里，作者报告了一种分子铁络合物，能够在催化过程中将氮还原为氨和联氨。
Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase. Converting dinitrogen into other nitrogen compounds such as ammonia is a difficult task, especially under mild conditions. Here, the authors report a molecular iron complex capable of reducing dinitrogen to both ammonia and hydrazine in a catalytic process.